Ultraviolet radiation absorbing polymer composition

ABSTRACT

Disclosed is a method for preparing an ultraviolet radiation absorbing polymer composition comprising the polymer compound of formula 
                         
in an esterification/transesterification which method comprises the steps of reacting a polyglycerol intermediate of formula
 
                         
with a benzotriazole UV-chromophore comprising a complementary functional group of formula
 
                         
to form the polymer compound of formula (3).

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national stage application (under 35 U.S.C. § 371)of PCT/EP2017/074931, filed Oct. 2, 2017, which claims benefit ofEuropean Application No. 16192444.4, filed Oct. 5, 2016, both of whichare incorporated herein by reference in their entirety.

The present invention relates to a method for preparing an ultravioletradiation, absorbing polymer composition comprising the polymer compoundof formula (3) in an esterification/transesterification which methodcomprises the steps of reacting a polyglycerol intermediate (2) with abenzotriazole UV-chromophore (1) comprising a complementary functional,group to form the polymer compound (3) according to the followingreaction scheme:

wherein

-   -   A is hydrogen; or C₁-C₈alkyl; and    -   k is a number from 1 to 20; and    -   n and m, independently from each other are a number from 0 to        20; wherein at least one of m and n is ≥1.

The polymer compound of formula (3) represents a UV absorbing polyetherthat absorbs radiation in wavelengths between 290 and 400 nm. The UVabsorbing polyether has a weight average molecular weight (M), which maybe suitable for reducing or preventing the chromophore from absorbingthrough the skin. According to one preferred embodiment, a suitablemolecular weight for the UV absorbing polyether is M>500. In a morepreferred embodiment, M is in the range of about 500 to about 50,000. Inanother preferred embodiment, M is in the range of about 1,000 to about20,000, such as from about 1,000 to about 10,000.

Polyglycerol (CAS Registry Number 25618-55-7; 1, 2, 3-Propanetriol,homopolymer) is known as a versatile building block for sustainablecosmetic raw materials (Wenk, H. H.; Meyer, J.; SOFW Journal, 2009,volume 135, issue 8, pages 25-30).

Polyglycerol is an ether linked homopolymer of glycerol, which isavailable in different degrees of polymerization, where higher polymersare associated with increasing hydrophilicity and molecular weight.Although the idealized structure of polyglycerol—a 1,3-linked, linearpolymer—is rather simple, the reality is much more complex.Polyglycerols are mixtures of a number of structures, which are definedby oligomer distribution, degree of branching, and amount of cyclicstructures. Even products with the same average molecular weight maydiffer significantly in their properties.

The oligomerization of glycerol is a consecutive reaction, and completeconversion of glycerol favours formation of high molecular-weightglycerol oligo—and polymers.

The general structural formula for polyglycerol can be sketched asHOCH₂—CHOH—CH₂—O—[CH₂—CHOH—CH₂—O]_(n)—CH₂—CHOH—CH₂OH,   (2a)wherein

-   -   n=0 results in diglycerol,    -   n=1 in triglycerol, n=2 in tetraglycerol etc., including        branched isomers formed by reaction of secondary hydroxyls.

Beside linear polyglycerol, cyclic oligomers can be formed by furthercondensation (Diglycerin and hoehere Oligomere des Glycerins alsSynthesebausteine, Jakobson, G., Fette, Seifen Anstrichmittel, 1986,volume 88, pages 101-106).

With increase of molecular weight the hydroxyl number of polyglyceroldecreases (diglycerol comprises 4, triglycerol 5, tetraglycerol 6 etc.hydrox groups). In some embodiments, the glycerol-based composition isfractionated to produce the desired distribution of glycerol polymersand a desired hydroxyl value.

Detailed synthesis procedures for the preparation of polyglycerol aredescribed in WO2011098315, WO2015122770, WO2002036534, US20020058781,U.S. Pat. No. 6,620,904 and WO2007092407.

Preferred catalysts for the preparation of polyglycerin are K₂CO₃,Li₂CO₃, Na₂CO₃, KOH, NaOH, CH₃ONa, Ca(OH)₂, LiOH, MgCO₃, MgO, CaO,CaCO₃, ZnO, CsOH, Cs₂CO₃, NaHCO₃, CsHCO₃, SrO and BaO.

The reaction is preferably carried out between 230 and 260° C.

The benzotriazole derivatives according to formula (1) represent the UVchromophore moiety of the present ultraviolet radiation absorbingcomposition.

Most preferred compounds are Benzenepropanoic acid,3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy—, methyl estercorresponding to formula

(CAS Registry Number 84268-33-7); and

Benzenepropanoic acid,3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-correspondingto formula

(CAS Registry Number 84268-36-0).

The polymeric reaction product is composed of a complex combination ofdifferent molecules (complex reaction product).

This is further illustrated in formula (3a) representing a polymeric UVabsorber according to the present invention based on a polyglycerolbackbone containing 5 glycerol units (examples without limitation):

The glycerol backbone typically consists mainly of 3 to 10 glycerolunits, whereby the hydroxyl groups of the glycerol backbone arecovalently linked to the benzotriazole UV chromophore. It might bereasonably assumed, that primary hydroxyl groups (terminal units) reactfaster than secondary hydroxyl groups, which are less reactive forderivatization. Therefore, some secondary hydroxyl groups remainunreacted. The glycerol backbone consists of primarily linear andunbranched structure units. Branched isomers and higher molecularfractions including more than 10 glycerol units can be present.

Minor components e.g. Benzotriazole conjugates of cyclic glycerololigomers (examples without limitation):

The polymer composition comprising the compound of formula (3) ischaracterized as follows:

Mn > 500 Da, Mw > 1200 Da (GPC, calibrated MW distribution onpolystyrene) Benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-5- ≤1.0%(HPLC) (1,1-dimethylethyl)-4-hydroxy-, methyl ester: Benzenepropanoicacid, 3-(2H-benzotriazol-2-yl)-5- ≤1.0% (HPLC)(1,1-dimethylethyl)-4-hydroxy- Sum of concentration of Benzenepropanoicacid, 3- ≤1.0% (HPLC) (2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-, methyl ester and Benzenepropanoic acid,3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4- hydroxy-:UV-absorption: E 1% 1 cm (344 nm): >310 Amount of boundchromophores: >70% Tg (° C.): >50 (DSC)

The characterization of the polymer composition is carried out accordingto the chapter “Methods” below.

Residual catalyst from transesterification reaction (Tin-II-ethylhexanoate) <700 ppm or essentially free of Sn (IPC)

Solubility in Cetiol B: >30%

Solubility in Cetiol AB: >30%

In a preferred method of the present invention the water or alcoholwhich is formed during the reaction is removed by distillation duringthe esterification/transesterification reaction.

In a further preferred method of the present invention theesterification/transesterification is carried out at a temperature of160-270° C., more preferably at a temperature of 190-260° C.

In a further preferred method of the present invention theesterification/transesterification is carried out without any additionalsolvent.

In a further preferred method of the present invention theesterification/transesterification is carried out without additionalesterification/transesterification catalysts.

In a further preferred method of the present invention theesterification/transesterification is carried out under intermittent orconstant vacuum of less than 250 mbar, more preferably of less than 100mbar.

In a further preferred method of the present invention theesterification/transesterification is carried out at a temperature of190-260 ° C. for at least 26 h.

In a further preferred method of the present invention the polyglycerolcontains less than 5% of glycerol or linear and cyclic diglycerols.

In a further preferred method of the present invention the hydroxylvalue of polyglycerol is in the range between 700 and 1100, morepreferably between 750 and 900.

In a further preferred method of the present invention the UVchromophore is benzene propanoic acid,3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy— correspondingto formula (1b).

In a further preferred method of the present invention the UVchromophore is Benzenepropanoic acid,3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy—, methyl estercorresponding to formula (1a).

In a further preferred method of the present invention the finalreaction product is used without further purification.

In a further preferred method of the present invention 1 part ofpolyglycerol is reacted with 2.8-3.2 parts of Benzene propanoic acid,3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy—, methyl estercorresponding to formula (1a).

In another preferred method of the present invention 1 part ofpolyglycerol is reacted with 2.8-3.2 parts of Benzene propanoic acid,3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy— correspondingto formula (1b).

Ultraviolet radiation absorbing polymer compositions comprising thepolymer compound of formula (3) according to the present invention areespecially useful as sunscreen actives for the protection of organicmaterials that are sensitive to ultraviolet light, especially human andanimal skin and hair, against the action of UV radiation. Such UVfilters are therefore suitable as light-protective agents in cosmeticand pharmaceutical applications.

A typical cosmetic or pharmaceutical composition according to thepresent invention comprises from 0.1 to 50% by weight, preferably from0.5 to 20% by weight, based on the total weight of the composition , ofthe ultraviolet radiation absorbing polymer composition comprising thepolymer compound of formula (3) according to the present invention and acosmetically tolerable adjuvant.

The cosmetic composition according to the present invention can beprepared by physically mixing the the ultraviolet radiation absorbingpolymer composition with the adjuvant using customary methods, forexample by simply stirring together the individual components,especially by making use of the dissolution properties of already knowncosmetic UV absorbers, for example Ethylhexyl Methoxycinnamate. The UVabsorbers can be used, for example, without further treatment.

In addition to other properties, the cosmetic composition according tothe present invention can be used as a radical scavenger by reducingsignificantly the number of UV-induced free radicals in skin whenapplied in a suitable cosmetic carrier.

The cosmetic composition may comprise, in addition to the ultravioletradiation absorbing polymer composition according to the presentinvention, one or more further UV protective agents.

Therefore, the present invention relates to a cosmetic compositioncomprising a UV filter combination of

-   -   (a) a UV radiation absorbing polyglycerol benzotriazole        conjugate of formula (3);    -   (b) UV filters selected from        -   (b₁) an aqueous dispersion of            5,6,5′,6′-tetraphenyl-3,3′-(1,4-Phenylene)bis(1,2,4-Triazine)            corresponding to the formula

-   -   in particulate form; and        -   (b₂) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine;        -   (b₃) Butyl Methoxydibenzoylmethane;        -   (b₄) Diethylhexyl Butamido Triazone;        -   (b₅) Ethylhexyl Triazone;        -   (b₆) Diethylamino Hydroxy Benzoyl Hexyl Benzoate;        -   (b₇) Ethylhexyl Methoxycinnamate;        -   (b₈) Ethylhexyl Salicylate;        -   (b₉) Homosalate;        -   (b₁₀) Octocrylene;        -   (b₁₁) Methylene Bis-Benzotriazolyl Tetramethylbutylphenol;        -   (b₁₂) Phenylbenzimidazole Sulfonic Acid;        -   (b₁₃) Titanium Dioxide;        -   (b₁₄) Tris-Biphenyl Triazine;        -   (b₁₅)            (2-{4-[2-(4-Diethylamino-2-hydroxy-benzoyl)-benzoyl]-piperazine-1-carbonyl}-phenyl)-(4-diethylamino-2-hydroxy-phenyl)-methanone;        -   (b₁₆) BBDAPT; Benzoic acid,            4,4′-[[6-[[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]-1            disiloxanyl]propyl]amino]-1,3,5-triazine-2,4-diyl]diimino]bis—,            dibutyl ester;        -   (b₁₇) benzylidene malonates;        -   (b₁₈) merocyanine derivatives;        -   (b₁₉) Bis(butylbenzoate) diaminotriazine            aminopropylsiloxane;        -   (b₂₀) Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine)            encapsulated in a polymer matrix;        -   (b₂₁)            2-(2H-Benzotriazol-2-yl)-6-[(2-ethylhexyloxy)methyl]-4-methylphenol;            and        -   (b₂₂) 2-Propenoic acid, 3-(4-methoxyphenyl)—, 2-methylphenyl            ester; and        -   (b₂₃) Zinc oxide.    -   wherein said composition contains at least one of the UV filters        (b₁)-(b₂₃); and    -   wherein said composition also contains a pharmaceutically or        cosmetically acceptable excipient.

Tinosorb S, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine encapsulatedin a polymer matrix (b₂₀) is described in IP.com Journal (2009), 9(1B ),17 (Tinosorb S Aqua, BASF).

2-(2H-Benzotriazol-2-yl)-6-[(2-ethylhexyloxy)methyl]-4-methylphenol(b₂₁) corresponds to formula

2-Propenoic acid, 3-(4-methoxyphenyl)—, 2-methylphenyl ester (b₂₂)corresponds to formula

Preferably the UV filters (b₁₁) Methylene Bis-BenzotriazolylTetramethylbutylphenol, (b₁₄) Tris-Biphenyl Triazine and (b₁₅)(2-{4-[2-(4-Diethylamino-2-hydroxy-benzoyl)-benzoyl]-piperazine-1-carbonyl}-phenyl)-(4-diethylamino-2-hydroxy-phenyl)-methanoneare present in the cosmetic or pharmaceutical composition in theirmicronized state.

The Benzylidene malonates (b₁₇) preferably correspond to formula

wherein

-   -   R₁ is methyl; ethyl; propyl; or n-butyl;    -   if R₁ is methyl, then R is tert. butyl;

a radical of formula (UV-AD-4a)

or a radical of formula (UV-AD-4b)

wherein

-   -   R₂ and R_(3,) independently from each other are hydrogen; or        methyl;    -   R₄ is methyl; ethyl; or n-propyl;    -   R₅ and R₆ independently from each other are hydrogen; or        C₁-C₃alkyl;    -   if R₁ is ethyl; propyl; or n-butyl, then    -   R is isopropyl.

Most preferred benzylidene malonates (b₁₇) is the compound of formula

The Benzylidene malonates (b₁₇) and their use as UV filter in sunscreensare disclosed in detail in WO2010/136360 and WO2011/003774.

The cosmetic composition according to the present invention maycomprise, in addition to the UV absorber combination according to theinvention, one or more further UV protective agents of the followingsubstance classes:

-   -   p-aminobenzoic acid derivatives, salicylic acid derivatives,        benzophenone derivatives, 3-imidazol-4-yl acrylic acid and        esters; benzofuran derivatives, polymeric UV absorbers, camphor        derivatives, encapsulated UV absorbers, and        4,4-diphenyl-1,3-butadiene derivatives.

Special preference is given to the light-protective agents indicated inthe following Table 3:

TABLE 3 Suitable UV filter substances and adjuvants which can beadditionally used with the UV absorber Phenylene Bis-Diphenyltriazineaccording to the present invention Chemical Name CAS No.(+/−)-1,7,7-trimethyl-3-[(4-methylphenyl)methylene]bicyclo- 36861-47-9[2.2.1]heptan-2-one; p-methyl benzylidene camphor1,7,7-trimethyl-3-(phenylmethylene)bicyclo[2.2.1]heptan-2-one;15087-24-8 benzylidene camphor(2-Hydroxy-4-methoxyphenyl)(4-methylphenyl)methanone 1641-17-42,4-dihydroxybenzophenone 131-56-6 2,2′,4,4′-tetrahydroxybenzophenone131-55-5 2-Hydroxy-4-methoxy benzophenone; 131-57-72,2′-dihydroxy-4,4′-dimethoxybenzophenone 131-54-42,2′-Dihydroxy-4-methoxybenzophenone 131-53-3Alpha-(2-oxoborn-3-ylidene)toluene-4-sulphonic acid and its salts56039-58-8 (Mexoryl SL) MethylN,N,N-trimethyl-4-[(4,7,7-trimethyl-3-oxobicyclo[2,2,1]hept-2-52793-97-2 ylidene)methyl]anilinium sulphate (Mexoryl SO) Isopentylp-methoxycinnamate; isoamyl methoxy cinnamate 71617-10-2Menthyl-o-aminobenzoate 134-09-8 Menthyl salicylate 89-46-34-aminobenzoic acid 150-13-0 Benzoic acid, 4-amino-, ethyl ester,polymer with oxirane 113010-52-9 2-Propenamide,N-[[4-[(4,7,7-trimethyl-3-oxobicyclo[2.2.1]hept-2- 147897-12-9ylidene)methyl]phenyl]methyl]-, homopolymer Triethanolamine salicylate2174-16-5 3,3′-(1,4-phenylenedimethylene)bis[7,7-dimethyl-2-oxo-90457-82-2 bicyclo[2.2.1]heptane-1 methanesulfonic acid] (Cibafast H)Zinc oxide (primary particle size 20-100 nm) 1314-13-2 For example Zincoxide NDM, Zinc oxide Z-Cote HP1, Nanox Zinc oxide Benzoic acid,4,4′-[[6-[[4-[[(1,1-dimethylethyl)amino]carbonyl]- 154702-15-5phenyl]amino]1,3,5-triazine-2,4-diyl]diimino]bis-, bis(2-ethylhexyl)-ester; diethylhexyl butamido triazone (Uvasorb HEB) Phenol,2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3- 155633-54-8tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]-; drometrizoletrisiloxane (Mexoryl XL) Dimethicodiethylbenzalmalonate; Polysilicone 15(Parsol SLX) 207574-74-1 Benzenesulfonic acid,3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1- 92484-48-5 methylpropyl)-,monosodium salt (Tinogard HS) 1-Dodecanaminium,N-[3-[[4-(dimethylamino)benzoyl]amino]propyl]- 156679-41-3N,N-dimethyl-, salt with 4-methylbenzenesulfonic acid (1:1) (EscalolHP610) 1-Propanaminium, N,N,N-trimethyl-3-[(1-oxo-3-phenyl-2-propenyl)-177190-98-6 amino]-, chloride 1H-Benzimidazole-4,6-disulfonic acid,2,2′-(1,4-phenylene)bis- 170864-82-1 1,3,5-Triazine,2,4,6-tris(4-methoxyphenyl)- 7753-12-0 1,3,5-Triazine,2,4,6-tris[4-[(2-ethylhexyl)oxy]phenyl]- 208114-14-1 1-Propanaminium,3-[[3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethyl- 340964-15-0ethyl)-4-hydroxyphenyl]-1-oxopropyl]amino]-N,N-diethyl-N-methyl-, methylsulfate (salt) 2-Propenoic acid, 3-(1H-imidazol-4-yl)- 104-98-3 Benzoicacid, 2-hydroxy-, [4-(1-methylethyl)phenyl]methyl ester 94134-93-71,2,3-Propanetriol, 1-(4-aminobenzoate) (Glyceryl PABA) 136-44-7Benzeneacetic acid, 3,4-dimethoxy-a-oxo- 4732-70-1 2-Propenoic acid,2-cyano-3,3-diphenyl-, ethyl ester 5232-99-5 Anthralinic acid,p-menth-3-yl ester 134-09-82,2′-bis(1,4-phenylene)-1H-benzimidazole-4,6-disulphonic acid mo-349580-12-7 no sodium salt or Disodium phenyl dibenzimidazoletetrasulfonate (Neo Heliopan AP) sterols (cholesterol, lanosterol,phytosterols), as described in WO0341675 mycosporines and/ormycosporine-like amino acids as described in WO2002039974, e.g.Helioguard 365 from Milbelle AG, isolated mycosporine like amino acidsfrom the red alga porphyra umbilicalis (INCI: Porphyra Umbilicalis) thatare encapsulated into liposomes) alpha-lipoic-acid as described in DE10229995 synthetic organic polymers as described in EP 1 371 358,[0033]-[0041] phyllosilicates as described in EP 1371357 [0034]-[0037]silica compounds as described in EP1371356, [0033]-[0041] inorganicparticles as described in DE10138496 [0043]-[0055] latex particles asdescribed in DE10138496 [0027]-[0040] 1H-Benzimidazole-4,6-disulfonicacid, 2,2′-(1,4-phenylene)bis-, 180898-37-7 disodium salt;Bisimidazylate (Neo Heliopan APC)Di-2-ethylhexyl-3,5-dimethoxy-4-hydroxy-benzalmalonate (Oxynex ST, EMDChemicals, as described in US 20040247536) Z-COTE ® MAX: Zinc Oxide(and) Diphenyl Capryl Methicone Z-COTE HP1: Zinc Oxide (and)Triethoxycaprylylsilane 1,3,5-Triazine-2,4,6-triamine,N2,N4-bis[4-[5-(1,1-dimethylpropyl)-2- 288254-16-0benzoxazolyl]phenyl]-N6-(2-ethylhexyl)- (Uvasorb K2A)1,1-[(2,2′-Dimethylpropoxy)carbonyl]-4,4-diphenyl-1,3-butadiene363602-15-7 UV filter capsules containing an organic sunscreen asdescribed in DE102007035567 or WO 2009012871

If the compositions according to the present invention represent water-and oil-containing emulsions (e.g. W/O, OW, O/W/O and W/O/W emulsions ormicroemulsions) they contain, for example, from 0.1 to 30% by weight,preferably from 0.1 to 15% by weight and especially from 0.5 to 10% byweight, based on the total weight of the composition, of the ultravioletradiation absorbing polymer compound of formula (3), from 1 to 60% byweight, especially from 5 to 50% by weight and preferably from 10 to 35%by weight, based on the total weight of the composition, of at least oneoil component, from 0 to 30% by weight, especially from 1 to 30% byweight and preferably from 4 to 20% by weight, based on the total weightof the composition, of at least one emulsifier, from 10 to 90% byweight, especially from 30 to 90% by weight, based on the total weightof the composition, of water, and from 0 to 88.9% by weight, especiallyfrom 1 to 50% by weight, of further cosmetically tolerable adjuvants.

Suitable oil components of oil-containing compositions (e.g. oils, W/O,O/W, O/W/O and W/O/W emulsions or microemulsions) are for exampleGuerbet alcohols based on fatty alcohols having from 6 to 18, preferablyfrom 8 to 10, carbon atoms, esters of linear C₆-C₂₄ fatty acids withlinear C₃-C₂₄ alcohols, esters of branched C₆-C₁₃carboxylic acids withlinear C₆-C₂₄ fatty alcohols, esters of linear C₆-C₂₄ fatty acids withbranched alcohols, especially 2-ethylhexanol, esters ofhydroxycarboxylic acids with linear or branched C₆-C₂₂ fatty alcohols,especially dioctyl malates, esters of linear and/or branched fatty acidswith polyhydric alcohols (for example propylene glycol, dimer diol ortrimer triol) and/or Guerbet alcohols, triglycerides based on C₆-C₁₀fatty acids, liquid mono-/di-/tri-glyceride mixtures based on C₆-C₁₈fatty acids, esters of C₆-C₂₄ fatty alcohols and/or Guerbet alcoholswith aromatic carboxylic acids, especially benzoic acid, esters ofC₂-C₁₂dicarboxylic acids with linear or branched alcohols having from 1to 22 carbon atoms or polyols having from 2 to 10 carbon atoms and from2 to 6 hydroxy groups, vegetable oils (such as sunflower oil, olive oil,soy-bean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheatgerm oil, peach kernel oil and the liquid components of coconut oil),branched primary alcohols, substituted cyclohexanes, linear and branchedC₆-C₂₂ fatty alcohol carbonates, Guerbet carbonates, esters of benzoicacid with linear and/or branched C₆-C₂₂alcohols (e.g. Finsolv® TN),linear or branched, symmetric or asymmetric dialkyl ethers having atotal of from 12 to 36 carbon atoms, especially from 12 to 24 carbonatoms, for example di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether,di-n-undecyl ether, di-n-dodecyl ether, n-hexyl n-octyl ether, n-octyln-decyl ether, n-decyl n-undecyl ether, n-undecyl n-dodecyl ether,n-hexyl n-undecyl ether, di-tert-butyl ether, diisopentyl ether,di-3-ethyldecyl ether, tert-butyl n-octyl ether, isopentyl n-octyl etherand 2-methyl pentyl-n-octyl ether; ring-opening products of epoxidisedfatty acid esters with polyols, silicone oils and/or aliphatic ornaphthenic hydrocarbons. Also of importance are monoesters of fattyacids with alcohols having from 3 to 24 carbon atoms. That group ofsubstances comprises the esterification products of fatty acids havingfrom 8 to 24 carbon atoms, for example caproic acid, caprylic acid,2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid,myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearicacid, oleic acid, elaidic acid, petroselinic acid, linoleic acid,linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid,behenic acid and erucic acid and technical-grade mixtures thereof(obtained, for example, in the pressure removal of natural fats andoils, in the reduction of aldehydes from Roelen's oxosynthesis or in thedimerisation of unsaturated fatty acids) with alcohols, for exampleisopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexylalcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristylalcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearylalcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linoylalcohol, linolenyl alcohol, elaeostearyl alcohol, arachidyl alcohol,gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcoholand technical-grade mixtures thereof (obtained, for example, in thehigh-pressure hydrogenation of technical-grade methyl esters based onfats and oils or aldehydes from Roelen's oxosynthesis and as monomerfractions in the dimerisation of unsaturated fatty alcohols). Of specialimportance are isopropyl myristate, isononanoic acid C₁₆-C₁₈alkylesters, stearic acid 2-ethylhexyl ester, cetyl oleate, glyceroltricaprylate, coconut fatty alcohol caprinate/caprylate and n-butylstearate. Further oil components that can be used are dicarboxylic acidesters, such as di-n-butyl adipate, di(2-ethylhexyl) adipate,di(2-ethylhexyl) succinate and diisotridecyl acetate, and also diolesters, such as ethylene glycol dioleate, ethylene glycoldiisotridecanoate, propylene glycol di(2-ethylhexanoate), propyleneglycol diisostearate, propylene glycol dipelargonate, butanedioldiisostearate and neopentyl glycol dicaprylate. Preferred mono- orpoly-ols are ethanol, isopropanol, propylene glycol, hexylene glycol,glycerol and sorbitol. It is also possible to use di- and/or trivalentmetal salts (alkaline earth metal, Al³⁺ inter alia) of one or more alkylcarboxylic acids.

The oil components can be used in an amount of, for example, from 1 to60% by weight, especially from 5 to 50% by weight and preferably from 10to 35% by weight, based on the total weight of the composition.

Any conventionally emulsifier can be used for the cosmetic compositionsaccording to the present invention.

Suitable emulsifiers are for example, non-ionic surfactants from thefollowing groups:

-   -   addition products of from 2 to 30 mol of ethylene oxide and/or        from 0 to 5 mol of propylene oxide with linear fatty alcohols        having from 8 to 22 carbon atoms, with fatty acids having from        12 to 22 carbon atoms and with alkylphenols having from 8 to 15        carbon atoms in the alkyl group, for example ceteareth-20 or        ceteareth-12;    -   C₁₂-C₂₂ fatty acid mono- and di-esters of addition products of        from 1 to 30 mol of ethylene oxide with polyols having from 3 to        6 carbon atoms, especially with glycerol;    -   glycerol mono- and di-esters and sorbitan mono- and di-esters of        saturated and unsaturated fatty acids having from 6 to 22 carbon        atoms and ethylene oxide addition products thereof, for example        glyceryl stearates, glyceryl isostearates, glyceryl oleates,        sorbitan oleates or sorbitan sesquioleates;    -   C₈-C₂₂alkyl-mono- and -oligo-glycosides and ethoxylated        analogues thereof, degrees of oligomerisation of from 1.1 to 5,        especially from 1.2 to 1.4, being preferred, and glucose being        preferred as the sugar component;    -   addition products of from 2 to 60 mol, especially from 15 to 60        mol, of ethylene oxide with castor oil and/or hydrogenated        castor oil;    -   polyol esters and especially polyglycerol esters, for example        diisostearoyl polyglyceryl-3-diisostearates,        polyglyceryl-3-diisostearates, triglyceryl diisostearates,        polyglyceryl-2-sesquiisostearates or polyglyceryl dimerates.        Mixtures of compounds from a plurality of those substance        classes are also suitable;    -   partial esters based on linear, branched, unsaturated or        saturated C₆-C₂₂ fatty acids, ricinoleic acid and also        12-hydroxystearic acid and on glycerol, polyglycerol,        pentaerythritol, dipentaerythritol, sugar alcohols (e.g.        sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl        glucoside, lauryl glucoside) and also polyglucosides (e.g.        cellulose), for example polyglyceryl-2-dihydroxystearates or        polyglyceryl-2-diricinoleates;    -   mono-, di- and tri-alkylphosphates and also mono-, di- and/or        tri-PEG-alkylphosphates and salts thereof;    -   wool wax alcohols;    -   one or more ethoxylated esters of natural derivatives, for        example polyethoxylated esters of hydrogenated castor oil;    -   silicone oil emulsifiers, for example silicone polyol;    -   polysiloxane/polyalkyl/polyether copolymers and corresponding        derivatives, for example cetyl dimethicone copolyol;    -   mixed esters of pentaerythritol, fatty acids, citric acid and        fatty alcohol (see DE-A-1 165 574) and/or mixed esters of fatty        acids having from 6 to 22 carbon atoms, methylglucose and        polyols, preferably glycerol or polyglycerol, for example        polyglyceryl-3-glucose distearates, polyglyceryl-3-glucose        dioleates, methyl glucose dioleates or dicocoyl pentaerythryl        distearyl citrates; and also    -   polyalkylene glycols.

The addition products of ethylene oxide and/or of propylene oxide withfatty alcohols, fatty acids, alkylphenols, glycerol mono- and di-estersand also sorbitan mono- and di-esters of fatty acids, or with castoroil, are known, commercially available products. They are usuallyhomologue mixtures, the average degree of alkoxylation of whichcorresponds to the ratio of the amounts of ethylene oxide and/orpropylene oxide and substrate with which the addition reaction iscarried out. C₁₂-C₁₈ fatty acid mono- and di-esters of addition productsof ethylene oxide with glycerol are known, for example, from DE-A-2 024051 as fat-restoring substances for cosmetic preparations.

C₈-C₁₈Alkyl-mono- and -oligo-glycosides, their preparation and their useare known from the prior art. They are prepared especially by reactingglucose or oligosaccharides with primary alcohols having from 8 to 18carbon atoms. Suitable glycoside radicals include monoglycol-sides inwhich a cyclic sugar radical is glycosidically bonded to the fattyalcohol and also oligomeric glycosides having a degree ofoligomerization of up to preferably about 8. The degree ofoligomerization is a statistical average value based on a homologuedistribution customary for such technical-grade products.

It is also possible to use zwitterionic surfactants as emulsifiers. Theterm “zwitterionic surfactants” denotes especially surface-activecompounds that carry at least one quaternary ammonium group and at leastone carboxylate and/or sulfonate group in the molecule. Zwitterionicsurfactants that are especially suitable are the so-called betaines,such as N-alkyl-N,N-dimethylammonium glycinates, for examplecocoalkyldimethylammonium glycinate,N-acylaminopropyl-N,N-dimethylammonium glycinates, for examplecocoacylaminopropyldimethylammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines each having from 8to 18 carbon atoms in the alkyl or acyl group and alsococoacylaminoethylhydroxyethylcarboxymethylglycinate. Special preferenceis given to the fatty acid amide derivative known by the CTFA namecocamidopropyl betaine. Likewise suitable as emulsifiers are ampholyticsurfactants. Ampholytic surfactants are to be understood as meaningespecially those which, in addition to containing a C₈-C₁₈-alkyl or-acyl group, contain at least one free amino group and at least one—COOH or —SO₃H group in the molecule and are capable of forming internalsalts. Examples of suitable ampholytic surfactants includeN-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids,N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines,N-alkyl-sarcosines, 2-alkylaminopropionic acids and alkylaminoaceticacids, each having approximately from 8 to 18 carbon atoms in the alkylgroup.

Ampholytic surfactants to which special preference is given areN-cocoalkylamino-propionate, cocoacylaminoethylaminopropionate andC₁₂-C₁₈acylsarcosine. In addition to the ampholytic emulsifiers therealso come into consideration quaternary emulsifiers, special preferenceis given to those of the esterquat type, preferably methyl-quaterniseddi-fatty acid triethanolamine ester salts.

Non-ionic emulsifiers are preferred, preferably ethoxylated fattyalcohols having from 8 to 22 carbon atoms and from 4 to 30 EO units.

The emulsifiers may be used in an amount of, for example, from 1 to 30%by weight, especially from 4 to 20% by weight and preferably from 5 to10% by weight, based on the total weight of the composition. It is,however, also possible in principle to dispense with the use ofemulsifiers.

The compositions according to the invention, for example creams, gels,lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fatcompositions, stick preparations, powders or ointments, may in additioncontain, as further adjuvants and additives, mild surfactants,super-fatting agents, pearlescent waxes, consistency regulators,thickeners, polymers, silicone compounds, fats, waxes, stabilisers,biogenic active ingredients, deodorising active ingredients,anti-dandruff agents, film formers, swelling agents, antioxidants,hydrotropic agents, preservatives, insect repellents, self-tanningagents, solubilizers, perfume oils, colorants, bacteria-inhibitingagents and the like.

Substances suitable for use as super-fatting agents are, for example,lanolin and lecithin and also polyethoxylated or acrylated lanolin andlecithin derivatives, polyol fatty acid esters, monoglycerides and fattyacid alkanolamides, the latter simultaneously acting as foamstabilisers.

Examples of suitable mild surfactants, that is to say surfactantsespecially well tolerated by the skin, include fatty alcohol polyglycolether sulfates, monoglyceride sulfates, mono- and/or di-alkylsulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fattyacid taurides, fatty acid glutamates, α-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides,alkylamidobetaines and/or protein fatty acid condensation products, thelatter preferably being based on wheat proteins.

Suitable pearlescent are for example: alkylene glycol esters, especiallyethylene glycol distearate; fatty acid alkanolamides, especially cocofatty acid diethanolamide; partial glycerides, especially stearic acidmonoglyceride; esters of polyvalent, unsubstituted orhydroxy-substituted carboxylic acids with fatty alcohols having from 6to 22 carbon atoms, especially long-chained esters of tartaric acid;fatty substances, for example fatty alcohols, fatty ketones, fattyaldehydes, fatty ethers and fatty carbonates, which in total have atleast 24 carbon atoms, especially laurone and distearyl ether; fattyacids, such as stearic acid, hydroxystearic acid or behenic acid,ring-opening products of olefin epoxides having from 12 to 22 carbonatoms with fatty alcohols having from 12 to 22 carbon atoms and/orpolyols having from 2 to 15 carbon atoms and from 2 to 10 hydroxygroups, and mixtures thereof.

Suitable consistency regulators are especially fatty alcohols or hydroxyfatty alcohols having from 12 to 22 carbon atoms and preferably from 16to 18 carbon atoms, and in addition partial glycerides, fatty acids andhydroxy fatty acids. Preference is given to a combination of suchsubstances with alkyl-oligoglucosides and/or fatty acidN-methylglucamides of identical chain length and/or polyglycerolpoly-12-hydroxystearates. Suitable thickeners include, for example,Aerosil types (hydrophilic silicic acids), polysaccharides, especiallyxanthan gum, guar-guar, agar-agar, alginates and Tyloses, carboxymethylcellulose and hydroxymethyl cellulose, also relatively high molecularweight polyethylene glycol mono- and di-esters of fatty acids,polyacrylates (e.g. Carbopol® from Goodrich or Synthalen® from Sigma),polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone,surfactants, for example ethoxylated fatty acid glycerides, esters offatty acids with polyols, for example pentaerythritol ortrimethyloipropane, fatty alcohol ethoxylates with restricted homologuedistribution and alkyloligoglucosides as well as electrolytes, such assodium chloride or ammonium chloride.

Suitable cationic polymers are, for example, cationic cellulosederivatives, for example a quarternised hydroxymethyl celluloseobtainable under the name Polymer JR 400® from Amerchol, cationicstarch, copolymers of diallylammonium salts and acrylamides,quarternised vinylpyrrolidone/vinyl imidazole polymers, for exampleLuviquat® (BASF), condensation products of polyglycols and amines,quaternised collagen polypeptides, for example lauryldimoniumhydroxypropyl hydrolyzed collagen (Lamequat®L/Grünau), quarternisedwheat polypeptides, polyethyleneimine, cationic silicone polymers, forexample amidomethicones, copolymers of adipic acid anddimethylaminohydroxypropyldiethylenetriamine (Cartaretin®/Sandoz),copolymers of acrylic acid with dimethyldiallylammonium chloride(Merquat® 550/Chemviron), polyaminopolyamides, as described, forexample, in FR-A-2 252 840, and the crosslinked water-soluble polymersthereof, cationic chitin derivatives, for example quaternised chitosan,optionally distributed as microcrystals; condensation products ofdihaloalkyls, for example dibromobutane, with bisdialkylamines, forexample bisdimethylamino-1,3-propane, cationic guar gum, for exampleJaguar® C-17, Jaguar® C-16 from Celanese, quaternised ammonium saltpolymers, for example Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 fromMiranol.

Suitable anionic, zwitterionic, amphoteric and non-ionic polymers arefor example, vinyl acetate/crotonic acid copolymers,vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butylmaleate/isobornyl acrylate copolymers, methyl vinyl ether/maleicanhydride copolymers and esters thereof, uncrosslinked polyacrylic acidsand polyacrylic acids crosslinked with polyols,acrylamidopropyltrimethylammonium chloride/acrylate copolymers, octylacrylamide/methyl methacrylate/tert-butylaminoethylmethacrylate/2-hydroxypropyl methacrylate copolymers,polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers,vinylpyrrolidone/dimethylaminoethyl methacrylate/vinyl caprolactamterpolymers and also optionally derivatised cellulose ethers andsilicones.

Suitable silicone compounds are, for example, dimethylpolysiloxanes,methylphenylpolysiloxanes, cyclic silicones, and also amino-, fattyacid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/oralkyl-modified silicone compounds, which at room temperature may be ineither liquid or resinous form. Also suitable are simethicones, whichare mixtures of dimethicones having an average chain length of from 200to 300 dimethylsiloxane units with hydrogenated silicates. A detailedsurvey by Todd et al. of suitable volatile silicones may in addition befound in Cosm. Toil. 91, 27 (1976).

Typical examples of fats are glycerides, and as waxes there come intoconsideration, inter alia, beeswax, carnauba wax, candelilla wax, montanwax, paraffin wax, hydrogenated castor oils and fatty acid esters ormicrowaxes solid at room temperature optionally in combination withhydrophilic waxes, e.g. cetylstearyl alcohol or partial glycerides.Metal salts of fatty acids, for example magnesium, aluminium and/or zincstearate or ricinoleate, may be used as stabilizers.

Biogenic active ingredients are for example, tocopherol, tocopherolacetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid,retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, aminoacids, ceramides, pseudoceramides, essential oils, plant extracts andvitamin complexes.

Suitable deodorizing active ingredients are for example, antiperspirantslike aluminium chlorohydrates (see J. Soc. Cosm. Chem. 24, 281 (1973)).Aluminium chlorohydrate corresponding to formula Al₂(OH)₅Cl×2.5 H₂O,known and commercially available under the trade mark Locron® of HoechstAG, Frankfurt (FRG), is especially preferred (see J. Pharm. Pharmacol.26, 531 (1975)). Beside the chlorohydrates, it is also possible to usealuminium hydroxy-acetates and acidic aluminium/zirconium salts.Esterase inhibitors may be added as further deodorising activeingredients. Such inhibitors are preferably trialkyl citrates, such astrimethyl citrate, tripropyl citrate, triisopropyl citrate, tributylcitrate and especially triethyl citrate (Hydagen® CAT, Henkel KGaA,Düsseldorf/FRG), which inhibit enzyme activity and hence reduce odourformation. Further suitable esterase inhibitors are sterol sulfates orphosphates, for example lanosterol, cholesterol, campesterol,stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids andesters thereof, for example glutaric acid, glutaric acid monoethylester, glutaric acid diethyl ester, adipic acid, adipic acid monoethylester, adipic acid diethyl ester, malonic acid and malonic acid diethylester and hydroxycarboxylic acids and esters thereof, for example citricacid, malic acid, tartaric acid or tartaric acid diethyl ester.Antibacterial active ingredients that influence the microbial flora andkill, or inhibit the growth of, sweat-decomposing bacteria can likewisebe present in the preparations (especially in stick preparations).Examples include chitosan, phenoxyethanol and chlorhexidine gluconate.5-Chloro-2-(2,4-dichlorophenoxy)-phenol (Irgasan®, BASF has also provedespecially effective.

Suitable anti-dandruff agents are for example, climbazole, octopirox andzinc pyrithione. Customary film formers include, for example, chitosan,microcrystalline chitosan, quaternised chitosan, polyvinylpyrrolidone,vinylpyrrolidone/vinyl acetate copolymers, polymers of quaternarycellulose derivatives containing a high proportion of acrylic acid,collagen, hyaluronic acid and salts thereof and similar compounds.Suitable swelling agents for aqueous phases are montmorillonites, claymineral substances, Pemulen and also alkyl-modified types of Carbopol(Goodrich). Further suitable polymers and swelling agents can be foundin the review by R. Lochhead in Cosm. Toil. 108, 95 (1993).

In addition to the primary light-protective substances it is alsopossible to use secondary light-protective substances of the antioxidanttype which interrupt the photochemical reaction chain triggered when UVradiation penetrates the skin or hair. Typical examples of suchantioxidants are amino acids (e.g. glycine, histidine, tyrosine,tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) andderivatives thereof, peptides, such as D,L-carnosine, D-carnosine,L-carnosine and derivatives thereof (e.g. anserine), carotinoids,carotenes (e.g. α-carotene, β-carotene, lycopene) and derivativesthereof, chlorogenic acid and derivatives thereof, lipoic acid andderivatives thereof (e.g. dihydrolipoic acid), aurothioglycose,propylthiouracil and other thiols (e.g. thioredoxin, glutathione,cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl,propyl, amyl, butyl, lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryland glyceryl esters thereof) and also salts thereof, dilaurylthiodipropionate, distearyl thiodipropionate, thiodipropionic acid andderivatives thereof (esters, ethers, peptides, lipids, nucleotides,nucleosides and salts) and also sulfoximine compounds (e.g. buthioninesulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-,hexa-, hepta-thionine sulfoximine) in very small tolerable amounts (e.g.from pmol to μmol/kg), also (metal) chelating agents (e.g. α-hydroxyfatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids(e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bileextracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof,unsaturated fatty acids and derivatives thereof (e.g. γ-linolenic acid,linoleic acid, oleic acid), folic acid and derivatives thereof,ubiquinone and ubiquinol and derivatives thereof, vitamin C andderivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate,ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate),vitamin A and derivatives (e.g. vitamin A palmitate) and also coniferylbenzoate of benzoin resin, rutinic acid and derivatives thereof,α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butyl hydroxyanisole, resinous nordihydroguaiareticacid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid andderivatives thereof, mannose and derivatives thereof, superoxidedismutase, N-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]sulfanilicacid (and salts thereof, for example the sodium salts), zinc andderivatives thereof (e.g. ZnO, ZnSO₄), selenium and derivatives thereof(e.g. selenium methionine), stilbene and derivatives thereof (e.g.stilbene oxide, trans-stilbene oxide) and the derivatives suitableaccording to the invention (salts, esters, ethers, sugars, nucleotides,nucleosides, peptides and lipids) of those mentioned active ingredients.HALS (=“Hindered Amine Light Stabilizers”) compounds may also bementioned. The amount of antioxidants present is usually from 0.001 to30% by weight, preferably from 0.01 to 3% by weight, based on the weightof the cosmetic composition according to the present invention.

For improvement of the flow behavior it is also possible to employhydrotropic agents, for example ethanol, isopropyl alcohol or polyols.Suitable polyols for that purpose comprise preferably from 2 to 15carbon atoms and at least two hydroxy groups.

The polyols may also contain further functional groups, especially aminogroups, and/or may be modified with nitrogen. Typical examples are asfollows:

-   -   glycerol;    -   alkylene glycols, for example ethylene glycol, diethylene        glycol, propylene glycol, butylene glycol, hexylene glycol and        also polyethylene glycols having an average molecular weight of        from 100 to 1000 dalton;    -   technical oligoglycerol mixtures having an intrinsic degree of        condensation of from 1.5 to 10, for example technical diglycerol        mixtures having a diglycerol content of from 40 to 50% by        weight;    -   methylol compounds, such as, especially, trimethylolethane,        trimethylolpropane, trimethyl-olbutane, pentaerythritol and        dipentaerythritol;    -   lower alkyl-glucosides, especially those having from 1 to 8        carbon atoms in the alkyl radical, for example methyl and butyl        glucoside;    -   sugar alcohols having from 5 to 12 carbon atoms, for example        sorbitol or mannitol;    -   sugars having from 5 to 12 carbon atoms, for example glucose or        saccharose;    -   amino sugars, for example glucamine;    -   dialcohol amines, such as diethanolamine or        2-amino-1,3-propanediol.

Suitable preservatives include, for example, phenoxyethanol,formaldehyde solution, Parabens, pentanediol or sorbic acid and thefurther substance classes listed in Schedule 6, Parts A and B of theCosmetics Regulations.

Suitable perfume oils are mixtures of natural and/or synthetic aromaticsubstances. Representatives of natural aromatic substances are, forexample, extracts from blossom (lilies, lavender, roses, jasmine,neroli, ylang-ylang), from stems and leaves (geranium, patchouli,petitgrain), from fruit (aniseed, coriander, carraway, juniper), fromfruit peel (bergamot, lemons, oranges), from roots (mace, angelica,celery, cardamom, costus, iris, calmus), from wood (pinewood,sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses(tarragon, lemon grass, sage, thyme), from needles and twigs (spruce,pine, Scots pine, mountain pine), from resins and balsams (galbanum,elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials alsocome into consideration, for example civet and castoreum. Typicalsynthetic aromatic substances are, for example, products of the ester,ether, aldehyde, ketone, alcohol or hydrocarbon type.

Aromatic substance compounds of the ester type are, for example, benzylacetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate,linalyl acetate, dimethyl-benzylcarbinyl acetate, phenylethyl acetate,linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate,allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.The ethers include, for example, benzyl ethyl ether; the aldehydesinclude, for example, the linear alkanals having from 8 to 18hydrocarbon atoms, citral, citronellal, citronellyl oxyacetaldehyde,cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal; theketones include, for example, the ionones, α-isomethylionone and methylcedryl ketone; the alcohols include, for example, anethol, citronellol,eugenol, isoeugenol, geraniol, linalool, phenyl ethyl alcohol andterpinol; and the hydrocarbons include mainly the terpenes and balsams.It is preferable, however, to use mixtures of various aromaticsubstances that together produce an attractive scent. Ethereal oils ofrelatively low volatility, which are chiefly used as aroma components,are also suitable as perfume oils, e.g. sage oil, camomile oil, cloveoil, melissa oil, oil of cinnamon leaves, lime blossom oil, juniperberry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil andlavandin oil. Preference is given to the use of bergamot oil,dihydromyrcenol, lilial, lyral, citronellol, phenyl ethyl alcohol,a-hexyl cinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde,linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemonoil, tangerine oil, orange oil, allyl amyl glycolate, cyclovertal,lavandin oil, muscatel sage oil, β-damascone, bourbon geranium oil,cyclohexyl salicylate, vertofix coeur, iso-E-Super, Fixolide NP,evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzylacetate, rose oxide, romillat, irotyl and floramat alone or in admixturewith one another.

As colourants the substances that are suitable and permitted forcosmetic purposes, as compiled, for example, in the publication“Kosmetische Färbemittel” of the Farbstoffkommission der DeutschenForschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106may be used. The colourants are usually used in concentrations of from0.001 to 0.1% by weight, based on the total mixture.

Typical examples of bacteria-inhibiting agents are preservatives thathave a specific action against gram-positive bacteria, such as2,4,4′-trichloro-2′-hydroxydiphenyl ether, chlorhexidine(1,6-di(4-chlorophenyl-biguanido)hexane) or TCC(3,4,4′-trichlorocarbanilide).

A large number of aromatic substances and ethereal oils also haveantimicrobial properties. Typical examples are the active ingredientseugenol, menthol and thymol in clove oil, mint oil and thyme oil. Anatural deodorizing agent of interest is the terpene alcohol farnesol(3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in limeblossom oil. Glycerol monolaurate has also proved to be a bacteriostaticagent. The amount of the additional bacteria-inhibiting agents presentis usually from 0.1 to 2% by weight, based on the solids content of thecosmetic composition according to the present invention.

The cosmetic compositions according to the present invention mayfurthermore contain as adjuvants anti-foams, such as silicones,structurants, such as maleic acid, solubilizers, such as ethyleneglycol, propylene glycol, glycerol or diethylene glycol, opacifiers,such as latex, styrene/PVP or styrene/acrylamide copolymers, complexingagents, such as EDTA, NTA, β-alaninediacetic acid or phosphonic acids,propellants, such as propane/butane mixtures, N₂O, dimethyl ether, CO₂,N₂ or air, so-called coupler and developer components as oxidation dyeprecursors, thioglycolic acid and derivatives thereof , thiolactic acid,cysteamine, thiomalic acid or α-mercaptoethanesulfonic acid as reducingagents or hydrogen peroxide, potassium bromate or sodium bromate asoxidizing agents.

Insect repellents are for example, N,N-diethyl-m-toluamide,1,2-pentanediol or insect repellent 3535.

Suitable self-tanning agents are dihydroxyacetone, erythrulose ormixtures of dihydroxyacetone and erythrulose.

Cosmetic formulations according to the invention are contained in a widevariety of cosmetic preparations, especially the following preparations:

-   -   skin-care preparations, e.g. skin-washing and cleansing        preparations in the form of tablet-form or liquid soaps,        synthetic detergents or washing pastes,    -   bath preparations, e.g. liquid (foam baths, milks, shower        preparations) or solid bath preparations, e.g. bath cubes and        bath salts;    -   skin-care preparations, e.g. skin emulsions, multi-emulsions or        skin oils;    -   cosmetic personal care preparations, e.g. facial make-up in the        form of day creams or powder creams, face powder (loose or        pressed), rouge or cream make-up, eye-care preparations, e.g.        eye shadow preparations, mascara, eyeliner, eye creams or        eye-fix creams; lip-care preparations, e.g. lipsticks, lip        gloss, lip contour pencils, nail-care preparations, such as nail        varnish, nail varnish removers, nail hardeners or cuticle        removers;    -   foot-care preparations, e.g. foot baths, foot powders, foot        creams or foot balsams, special deodorants and antiperspirants        or callus-removing preparations;    -   light-protective preparations, such as sun milks, lotions,        creams or oils, sunblocks or tropicals, pre-tanning preparations        or after-sun preparations;    -   skin-tanning preparations, e.g. self-tanning creams;    -   depigmenting preparations, e.g. preparations for bleaching the        skin or skin-lightening preparations;    -   insect-repellents, e.g. insect-repellent oils, lotions, sprays        or sticks;    -   deodorants, such as deodorant sprays, pump-action sprays,        deodorant gels, sticks or roll-ons;    -   antiperspirants, e.g. antiperspirant sticks, creams or roll-ons;    -   preparations for cleansing and caring for blemished skin, e.g.        synthetic detergents (solid or liquid), peeling or scrub        preparations or peeling masks;    -   hair-removal preparations in chemical form (depilation), e.g.        hair-removing powders, liquid hair-removing preparations, cream-        or paste-form hair-removing preparations, hair-removing        preparations in gel form or aerosol foams;    -   shaving preparations, e.g. shaving soap, foaming shaving creams,        non-foaming shaving creams, foams and gels, preshave        preparations for dry shaving, aftershaves or aftershave lotions;    -   fragrance preparations, e.g. fragrances (eau de Cologne, eau de        toilette, eau de parfum, parfum de toilette, parfume), parfume        oils or parfume creams;    -   cosmetic hair-treatment preparations, e.g. hair-washing        preparations in the form of shampoos and conditioners, hair-care        preparations, e.g. pre-treatment preparations, hair tonics,        styling creams, styling gels, pomades, hair rinses, treatment        packs, intensive hair treatments, hair-structuring preparations,        e.g. hair-waving preparations for permanent waves (hot wave,        mild wave, cold wave), hair-straightening preparations, liquid        hair-setting preparations, hair foams, hairsprays, bleaching        preparations, e.g. hydrogen peroxide solutions, lightening        shampoos, bleaching creams, bleaching powders, bleaching pastes        or oils, temporary, semi-permanent or permanent hair colourants,        preparations containing self-oxidising dyes, or natural hair        colourants, such as henna or camomile.

The final formulations may exist in a wide variety of presentationforms, for example:

-   -   in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W        or PIT emulsion and all kinds of microemulsions,    -   in the form of a gel,    -   in the form of an oil, a cream, milk or lotion,    -   in the form of a powder, a lacquer, a tablet or make-up,    -   in the form of a stick,    -   in the form of a spray (spray with propellant gas or pump-action        spray) or an aerosol,    -   in the form of a foam, or    -   in the form of a paste.

Important cosmetic compositions for the skin are light-protectivepreparations, such as sun milks, lotions, creams, oils, sunblocks ortropicals, pretanning preparations or after-sun preparations, alsoskin-tanning preparations, for example self-tanning creams. Ofparticular interest are sun protection creams, sun protection lotions,sun protection oils, sun protection milks and sun protectionpreparations in the form of a spray.

Important cosmetic compositions for the hair are the above-mentionedpreparations for hair treatment, especially hair-washing preparations inthe form of shampoos, hair conditioners, hair-care preparations, e.g.pretreatment preparations, hair tonics, styling creams, styling gels,pomades, hair rinses, treatment packs, intensive hair treatments,hair-straightening preparations, liquid hair-setting preparations, hairfoams and hairsprays. Of special interest are hair-washing preparationsin the form of shampoos.

A shampoo has, for example, the following composition:

-   -   0.01 to 5% by weight of a UV absorber composition according to        the invention,    -   12.0% by weight of sodium laureth-2-sulfate,    -   4.0% by weight of cocamidopropyl betaine,    -   3.0% by weight of sodium chloride, and    -   water ad 100%.

Especially the following hair-cosmetic formulations may be used:

-   -   a₁) spontaneously emulsifying stock formulation, consisting of        the UV absorber according to the invention, PEG-6-C₁₀oxoalcohol        and sorbitan sesquioleate, to which water and any desired        quaternary ammonium compound, for example 4%        minkamidopropyl-dimethyl-2-hydroxyethylammonium chloride or        Quaternium 80 is added;    -   a₂) spontaneously emulsifying stock formulation consisting of        the UV absorber according to the invention, tributyl citrate and        PEG-20-sorbitan monooleate, to which water and any desired        quaternary ammonium compound, for example 4%        minkamidopropyl-dimethyl-2-hydroxyethylammonium chloride or        Quaternium 80 is added;    -   b) Quat-doped solutions of the UV absorber according to the        invention in butyltriglycol and tributyl citrate;    -   c) mixtures or solutions of the UV absorber according to the        invention with n-alkylpyrrolidone.

The following examples are illustrative of the principles and practiceof the present invention, although not limited thereto.

Methods

Determination of3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoicacid and3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoicacid methyl ester by HPLC

Operation range: The concentration of both compounds can be determinedfrom 0.02% -10% w/w %.

Solvents: Water HPLC-quality, acetonitrile HPLC-quality,tetrahydrofurane HPLC-quality, tetrabutyl ammonium hydrogensulfate(TBAHS) HPLC-quality

Column: Eclipse XDB C8 4.6*150 mm 5 μm

Mobile phase A: Water—acetonitrile 9:1+TBAHS 2 g/l

Mobile phase B: Acetonitrile—tetrahydrofurane 1:1

Flow: 1.1 ml/min

Injection volume: 10 μl

Oven temperature: 50° C.

Detection wavelength: 302 nm

Gradient Time [min] A [%] B [%] 0 50 50 15 2 98 20 2 98 21 50 50 PostTime 5

Calibration: The quantification is carried by means of a single pointcalibration. About 10 mg of acid ester is weighted in a 100 ml brownvolumetric flask and filled up with tetrahydrofurane. The sample isdissolved in an ultrasonic bath for about 5 min and the solution isanalyzed. This solution is diluted 1:10 with THF.

Hydrolysis of Ultraviolet Radiation Absorbing Compositions

100 mg of the ultraviolet radiation absorbing composition is dissolvedin 100 ml of a solvent mixture (70 parts THF/30 parts 0.1N NaOH) and 2-3drops of water are added. The sample must be completely dissolved,otherwise a few drops of water have to be added. The mixture is heatedat 50° C. for 2 h in a drying cabinet. After cooling to roomtemperature, 1 ml of this solution is transferred to a 100 ml volumetricflask and filled up with THF. The content of3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoicacid is analyzed by HPLC.

Amount of Covalentely Bound Chromophore:

The amount of chromophore is calculated as w/w % of3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid.

The amount of covalentely bound chromophore is determined as follows:

HPLC analysis of the reaction product (determination of the unboundchromophore) Compound %3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene- Apropanoic acid methyl ester3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene- Epropanoic acid Sum S

HPLC analysis of the completely hydrolyzed reaction product(determination of the unbound and bound chromophore) Compound %3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene- Cpropanoic acid

Amount of Covalentely Bound Chromophore T (%):T=C−(A+E)=C−S

Determination of E (1%/1 cm) at 343 nm by UV spectroscopy:

Spectrophotometer Lamda 950 S (or equivalent)

Cell Type: Quarz, 10 mm

Reference: 1.4-dioxane

Temperature: ca.25° C.

Solvent: 1.4-dioxane, spectrophotometric grade

Preparation of the test solutions: About 25 mg of sample is weighed witha precision balance into a 100.0 ml (Vs) volumetric flask. It is filledup to the mark with 1.4-dioxane. 10.0 ml (V) of this solution is dilutedto 100.0 ml (Vf) with 1.4-dioxane. The absorbance of this solution ismeasured between 290 and 450 nm.

Calculation of E (1%/1 cm):

Weighing w=in mg

Total volume of stock solution Vs

Used volume of stock solution V

Final volume of solution Vf

Cell d=10 mm

Wavelength maximum λ=343 nm

Measured absorbance at 343 nm A

${E\left( {{1\%},{1\mspace{14mu}{cm}}} \right)} = {A_{m} \cdot \frac{{{Vs} \cdot {Vf}}*10}{w \cdot V}}$

Determination of methanol by headspace GC-MS

Standard: Methanol

Solvents: 1,3-Dimethyl-2-imidazolidinone=DMI

Autosampler: Agilent G 1888 Headspace

Temperature: Oven: 100° C. loop: 110° C. transfer Line: 130° C.

Shaking: High

Pressure (psi): Carrier: 17.8 Vial: 13.0

Timing (minutes) Vial Equil.: 30.0

Pressure: 3.00

Loop Fill: 0.20

Loop Equil.: 0.05

Inject: 1.00

Gas Chromatograph: Agilent 6890

Injection technique: Split, 30 ml He/min.

Column: DB-VRX, film thickness 1.4 μm, 60 m×0.25 mm

Carrier gas: He, 1.0 ml/min

Temperatures: Injector: 220° C.

Oven: 2 min 50° C.//10° C./min to 260° C.//isothermal 15 min

Detector: Agilent 5973 Inert Mass Selective detector

EM Volts: 1718

Solvent Delay: 0.00; detector off: 15.0 min

SIM Modus: Component Ions, methanol 31

A standard calibration curve is generated by plotting the concentrationof methanol vs. the peak area obtained.y=mx+b

y=peak area

m=slope

x=concentration of methanol (mg/100 ml)

b=y intercept

x (mg/100 ml)=(y−b)/m

Molecular weight distribution by GPC

Method: Gel Permeation Chromatography with RI-Detection

Standards: EasiVial GPC/SEC Calibration Standards PSS Part. No:PL2010-0201 Agilent

Solvents: Tetrahydrofurane HPLC quality, diethanolamine puriss p.a.

Apparatus: Malvern Viscotek with RI-Detector

Chromatography Conditions:

-   -   Column1: PSS SDV 100,000 A, 8×300 mm, 5 u    -   Column2: PSS SDV 1000 A, 8×300 mm, 5 u    -   Oven temperature: 40° C.    -   Mobile Phase: Tetrahydrofurane+3.7 g/L DEA    -   Flow: 1.0 ml/min    -   Sample concentration: approx. 2 mg/ml in the same solvent        mixture as the mobile phase.    -   Calibration: Conventional calibration homopolymeres.    -   Polystyrene reference samples.

Gardner Color

Spectral color measurement with Lange, LICO 300; 30% solution of theultraviolet radiation absorbing composition in dibutyl adipate (CetiolB).

Determination of the glass transition temperature (T_(g)) by DSC

Differential Scanning calorimeter (DSC 822e, Mettler Toledo), 40 μlaluminium crucible, micro scale (MX5, Mettler Toledo). The oven isnitrogen-purged.

Procedure: 3-7 mg sample is charged with the micro scale into analuminium crucible. The crucible is closed hermetically with analuminium cover. Two crucibles are prepared per sample. The preparedcrucible is put in the DSC equipment and the method is started asdescribed below.

First scan: −30° C. to 200° C., 10° C./min heating rate

Second scan: Cool to −30° C. with −10° C./min cooling rate

Third scan: −30° C. to 200° C., 10° C./min heating rate

The third scan is used for the determination of the glass transitiontemperature.

The mean of the glass transition temperature is calculated.

Determination of Sn by Inductively Coupled Plasma Atomic EmissionSpectrometry (ICP-AES).

The sample preparation is done by pressurized wet digestion in PTFEvessels: About 200 mg of the sample is treated with 3 ml HNO₃ at atemperature of about 150° C. for six hours and cooled down to roomtemperature. The obtained solution is diluted with deionized water to anend volume of 20 ml and directly measured by ICP-AES.

The calibration is done by external standard method with commerciallyavailable elemental standard solutions. As a typical apparatus a VarianVista Pro ICP-AES or Agilent 5100 ICP-AES spectrometer can be used.Specific wavelengths for evaluation: Sn, 189.924 nm for the quantitativeevaluation as well as 133, 138, 143, 146 and 284 nm to check possibleinterferences.

Determination of the Solubility in Cosmetic Solvents

800 mg of pulverized UV filter is suspended in 1200 mg solvent in aglass container. A magnetic stirring bar is added. The container isclosed and stirred over night at room temperature (20-30° C.). It hasalways to be checked that the stirrer does not stick to the glasscontainer.

Specification: clear or slightly turbid solution

Cosmetic solvents: Dicaprylyl carbonate (Cetiol CC, BASF), C12-15 alkylbenzoate (Cetiol AB, BASF), Dibutyl adipate (Cetiol B, BASF)

EXAMPLES

Polyglycerol

Polyglycerol is prepared as described in WO 2002 036534, US 2002 0058781and U.S. Pat. No. 6,620,904. CaO or Ca(OH)₂ is used as catalyst.Glycerol, diglycerol and other low molecular fractions are removed fromthe reaction product e.g. by short path distillation in order to achievea specific quality.

Properties of polyglycerol: yellow to brown material; very highviscosity at room temperature, hydroxyl-value 800-1000, water content<0.2%, glycerol and diglycerols <5.5% (determined by GC afterderivatization with a silylating agent).

Example A1 Transesterification Product of3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl-4-hydroxy-benzenepropanoicAcid with Polyglycerol

3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid (605.8 g) is charged into a glass reactor equipped with nitrogeninlet, dephlegmator (120° C.) and agitation. The temperature is set to227° C. in order to melt the3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid. As soon as the3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid is completely melted, tin-(II)-2-ethyl-hexanoate (0.48 g) is addedand the reactor is evacuated to 860 mbar. Molten polyglycerol (207.1 g)is charged within 1 h, while maintaining a reaction temperature of220-225° C. and a pressure of 30 mbar. Methanol is distilled of.Thereafter the vacuum is reduced gradually to 5-8 mbar at 225° C. andthe reaction mass is stirred for 16-18 h, until the total concentrationof3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid methyl ester and3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid is below 1.0%. The composition of the reaction mixture is monitoredby HPLC. After cooling down to ambient temperature, the UV-absorbingpolymer composition (756.3 g) is obtained as a yellow to amber glassysolid.

HPLC (unbound chromophore) Compound %3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid methyl ester3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoic acid Sum <1%a

Solubility Solvent % C12-15 alkyl benzoate >40 Dibutyl adipate >40Dicaprylyl carbonate >40

Example A2 Ultraviolet radiation absorbing composition:Transesterification product of3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoicAcid Methyl Ester with Polyglycerol

3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid methyl ester (630.9 g) is charged into a glass reactor equippedwith nitrogen inlet, dephlegmator (120° C.) and agitation. Thetemperature is set to 227° C. in order to melt the3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid methyl ester. As soon as the3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid methyl ester is completely melted, tin-(II)-2-ethylhexanoate (0.48g) is added and the reactor is evacuated to 860 mbar. Moltenpolyglycerol (206.9 g) is charged within 1 h, while maintaining areaction temperature of 220-225° C. and a pressure of 30 mbar. Methanolis distilled of. Thereafter the vacuum is reduced gradually to 5-8 mbarat 225° C. and the reaction mass is stirred for 16-18 h, until the totalconcentration of3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid methyl ester and3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid is below 1.0%.

The composition of the reaction mixture is monitored by HPLC. Aftercooling down to ambient temperature, the UV-absorbing polymercomposition (750.3 g) is obtained as a yellow to amber glassy solid.

HPLC (unbound chromophore) Compound %3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene- 0.2propanoic acid methyl ester3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene- 0.6propanoic acid Sum 0.8

UV Wave- E length (1%, Solubility GPC (nm) 1 cm) Solvent % Peak RV -(ml) 18.4 344 336 C12-15 alkyl benzoate >40 Dibutyl adipate >40 Mn -(Daltons) 872 Dicaprylyl carbonate >40 Mw - (Daltons) 1577 Mz -(Daltons) 2370 Mp - (Daltons) 1341 Mw/Mn 1.80

Example A3 Ultraviolet radiation absorbing composition:Transesterification product of3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoicAcid Methyl Ester with Polyglycerol

3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid methyl ester (630.84 g, 1.785 mol) is charged into a glass reactorequipped with nitrogen inlet, dephlegmator (120° C.) and agitation. Thetemperature is set to 197° C. in order to melt the3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid methyl ester. As soon as the3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid methyl ester is completely melted, tin-(II)-2-ethylhexanoate (0.47g, 1.2 mmol) is added and the reactor is evacuated to 850 mbar. Moltenpolyglycerol (206.3 g) is charged within 1 h, while maintaining areaction temperature of 185-190° C. Methanol is distilled of. Thereafterthe vacuum is reduced gradually to 5-8 mbar at 197° C. and the reactionmass is stirred for 48 h, until the total concentration of3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid methyl ester and3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid is below 1.0%. The composition of the reaction mixture is monitoredby HPLC. After cooling down to ambient temperature, the UV-absorbingpolymer composition (748.5 g) is obtained as a yellow to amber glassysolid.

HPLC (unbound chromophore) Compound %3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- 0.1benzene-propanoic acid methyl ester3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- 0.5benzene-propanoic acid Sum 0.6

UV Wave- E length (1%, Solubility GPC (nm) 1 cm) Solvent % Peak RV -(ml) 18.16 300 346 C12-15 alkyl benzoate >40 Mn - (Daltons) 911 320 284Dibutyl adipate >40 Mw - (Daltons) 1584 340 342 Dicaprylyl carbonate >40Mz - (Daltons) 2277 360 263 Mp - (Daltons) 1383 380 70 Mw/Mn 1.74 400 1344 345 343 345 303 351

Example A4 Ultraviolet Radiation Absorbing Composition:Transesterification product of3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoicAcid Methyl Ester with Polyglycerol

A 100 ml glass flask is placed in an agitating heating block andpolyglycerol (2.9 g) is transferred into the flask.3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid methyl ester (8.8 g, 25 mmol) and tin-(II)-2-ethylhexanoate (0.029g, 0.072 mmol) is added. The mixture is melted and heated up to 195° C.under a nitrogen flow. Thereafter the apparatus is slowly evacuated to apressure of 5 mbar. The reaction mixture is stirred vigorously undervacuum at 195° C. for approx. 16 h and at 250° C. for approx. 24 h.After cooling down to ambient temperature, the UV-absorbing polymercomposition (10.3 g) is obtained as a brown glassy solid.

HPLC (unbound chromophore) Compound %3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- 0benzene-propanoic acid methyl ester3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- 1.0benzene-propanoic acid Sum 1.0

Solubility GPC Solvent % Peak RV - (ml) 18.1 C12-15 alkyl benzoate >40Mn - (Daltons) 1679 Dibutyl adipate >40 Mw - (Daltons) 3160 Dicaprylylcarbonate >40 Mz - (Daltons) 5669 Mp - (Daltons) 1738 Mw/Mn 1.88

Example A5 Ultraviolet Radiation Absorbing Composition:Transesterification Product of3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoicAcid Methyl Ester with Polyglycerol

3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid methyl ester (1000.0 g) is charged into a glass reactor equippedwith nitrogen inlet, dephlegmator (120° C.) and agitation. Thetemperature is set to 191° C. in order to melt the3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid methyl ester. As soon as the3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid methyl ester is completely melted, the reactor is evacuated to 850mbar. Molten polyglycerol (325.7 g) is charged within 1 h, whilemaintaining a reaction temperature of 185-190° C. Methanol is distilledof. Thereafter the vacuum is reduced gradually to 5-8 mbar at 197° C.and the reaction mass is stirred for 44 h, until the total concentrationof3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid methyl ester and3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid is below 1.0%. The composition of the reaction mixture is monitoredby HPLC. After cooling down to ambient temperature, the UV-absorbingpolymer composition (1200 g) is obtained as a yellow to amber glassysolid.

HPLC (unbound chromophore) Compound %3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- 0.25benzene-propanoic acid methyl ester3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- 0.5benzene-propanoic acid Sum 0.75

UV Wavelength E Solubility (nm) (1%, 1 cm) Solvent % GPC 300 354 C12-15alkyl benzoate >40 Peak RV-(ml) 18.3 320 292 Dibutyl adipate >40Mn-(Daltons) 899 340 351 Dicaprylyl carbonate >40 Mw-(Daltons) 1573 360269 Mz-(Daltons) 2300 380  73 Mp-(Daltons) 1354 400  4 Mw/Mn 1.75 344354 344 354 303 359

Example A6 Ultraviolet Radiation Absorbing Composition:Transesterification Product of3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzenepropanoicAcid Methyl Ester with Polyglycerol

3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid methyl ester (306.0 kg) is charged into a glass-lined steel reactorequipped with argon inlet, dephlegmator (120° C.) and agitation. Thetemperature is set to 195° C. in order to melt the3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid methyl ester. As soon as the3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid methyl ester is completely melted, the reactor is evacuated to 850mbar and tin-(II)-2-ethylhexanoate (20.0 kg) is added. Moltenpolyglycerol (105.0 kg) is charged within 1-2 h, while maintaining areaction temperature of 185-190° C. Methanol is distilled of. Thereafterthe vacuum is reduced gradually to 5-8 mbar at 195° C. and the reactionmass is stirred for 72 h until the total concentration of3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid methyl ester and3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid is below 1.0%. The composition of the reaction mixture is monitoredby HPLC. After cooling down to ambient temperature, the UV-absorbingpolymer composition (384 kg) is obtained as a yellow to amber glassysolid.

HPLC analysis of the reaction product (unbound chromophore) Compound %3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- 0.1benzene-propanoic acid methyl ester3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- 0.5benzene-propanoic acid Sum 0.6

HPLC analysis of the completely hydrolized reaction product Compound %3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy- 75.8benzene-propanoic acid

Amount of Covalentely Bound Chromophore

75.8%−0.6%=75.2% (chromophore, determined as3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy-benzene-propanoicacid).

UV Solubility in E 1%, 1 cm cosmetic solvents GPC (λ = 344 nm) 331Solvent % Peak RV - (ml) 18.2 Methanol 6 C12-15 alkyl >40 (ppm) benzoateT_(g) (° C.) 51.2 Dibutyl adipate >40 Mn - (Daltons) 756 Sn (ppm) 150Dicaprylyl >40 Mw - (Daltons) 1464 carbonate Gardner 6.2 Mz - (Daltons)2153 color scale Mp - (Daltons) 1320 Mw/Mn 1.94

The invention claimed is:
 1. A method for preparing an ultravioletradiation absorbing polymer composition comprising a polymer compound offormula (3) in an esterification/trans-esterification, which methodcomprises the steps of reacting a polyglycerol intermediate (2) with abenzotriazole UV-chromophore (1) comprising a complementary functionalgroup to form the UV absorbing polyether compound (3) according to thefollowing reaction scheme:

wherein A is hydrogen; or C₁-C₈alkyl; and k is a number from 2 to 20;and n and m, independently from each other are a number from 0 to 20;wherein at least one of m and n is ≥1.
 2. The method according to claim1, wherein the weight average molecular weight of the polyether offormula (3) is >500.
 3. The method according to claim 1, furthercomprising removing water or alcohol formed during the reaction bydistillation during the esterification/transesterification reaction. 4.The method according to claim 1, wherein theesterification/transesterification is carried out at a temperature of160-270° C.
 5. The method according to claim 1, wherein theesterification/transesterification is carried out without any additionalsolvent.
 6. The method according to claim 1, wherein theesterification/transesterification is carried out without additionalesterification/transesterification catalysts.
 7. The method according toclaim 1, wherein the esterification/transesterification is carried outunder intermittent or constant vacuum of less than 250 mbar.
 8. Themethod according to claim 1, wherein theesterification/transesterification is carried out at a temperature of190-260 ° C. for at least 16h.
 9. The method according to claim 1,wherein the polyglycerol contains less than 5% of glycerol or linear andcyclic diglycerols.
 10. The method according to claim 1, wherein thehydroxyl value of polyglycerol is in the range between 700 and
 1100. 11.The method according to claim 1, wherein the benzotriazoleUV-chromophore is benzenepropanoic acid,3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy—.
 12. Themethod according to claim 1, wherein the benzotriazole UV-chromophore isbenzenepropanoic acid,3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy—,methyl ester.13. The method according to claim 1, wherein the final reaction productis used without further purification.
 14. The method according to claim12, wherein 1 part of polyglycerol is reacted with 2.8-3.2 parts ofBenzenepropanoic acid,3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy—, methyl ester.15. The method according to claim 11, wherein 1 part of polyglycerol isreacted with 2.8-3.2 parts of Benzenepropanoic acid,3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy—.
 16. Themethod according to claim 1, wherein the weight average molecular weightof the polyether of formula (3) is from 1,000 to 20,000.
 17. The methodaccording to claim 1, wherein the weight average molecular weight of thepolyether of formula (3) is from 1,000 to 10,000.
 18. The methodaccording to claim 1, wherein the esterification/transesterification iscarried out at a temperature of 190-260° C.
 19. The method according toclaim 1, wherein the esterification/transesterification is carried outunder intermittent or constant vacuum of less than 100 mbar.
 20. Themethod according to claim 1, wherein the hydroxyl value of polyglycerolis in the range between 750 and 900.